CA2048064A1 - Calcium-sequestering agents based on oxidised carbohydrates and their use as builders for detergents - Google Patents
Calcium-sequestering agents based on oxidised carbohydrates and their use as builders for detergentsInfo
- Publication number
- CA2048064A1 CA2048064A1 CA002048064A CA2048064A CA2048064A1 CA 2048064 A1 CA2048064 A1 CA 2048064A1 CA 002048064 A CA002048064 A CA 002048064A CA 2048064 A CA2048064 A CA 2048064A CA 2048064 A1 CA2048064 A1 CA 2048064A1
- Authority
- CA
- Canada
- Prior art keywords
- oligomers
- glucosidic
- oxidised
- hydrolytic
- polymerisation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000003599 detergent Substances 0.000 title claims abstract 7
- 150000001720 carbohydrates Chemical class 0.000 title 1
- 235000014633 carbohydrates Nutrition 0.000 title 1
- 239000003352 sequestering agent Substances 0.000 title 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229920002472 Starch Polymers 0.000 claims abstract description 4
- 235000019698 starch Nutrition 0.000 claims abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 8
- 230000003647 oxidation Effects 0.000 claims abstract 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract 5
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims abstract 4
- 229920001353 Dextrin Polymers 0.000 claims abstract 3
- 239000004375 Dextrin Substances 0.000 claims abstract 3
- 229910001919 chlorite Inorganic materials 0.000 claims abstract 3
- 229910052619 chlorite group Inorganic materials 0.000 claims abstract 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims abstract 3
- 235000019425 dextrin Nutrition 0.000 claims abstract 3
- 239000007800 oxidant agent Substances 0.000 claims abstract 3
- 230000002255 enzymatic effect Effects 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims 1
- 239000000539 dimer Substances 0.000 claims 1
- 150000008131 glucosides Chemical group 0.000 claims 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims 1
- 239000013638 trimer Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 101100114362 Caenorhabditis elegans col-7 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001487812 Crotophaga ani Species 0.000 description 1
- 101100046831 Drosophila melanogaster Tpst gene Proteins 0.000 description 1
- 241000947661 Lestis Species 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- DCERVXIINVUMKU-UHFFFAOYSA-N diclofenac epolamine Chemical compound OCC[NH+]1CCCC1.[O-]C(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCERVXIINVUMKU-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Emergency Medicine (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Detergent Compositions (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Cosmetics (AREA)
Abstract
ABSTRACT
A mixture including oxidised glucosidic oligomers including at least 60% by weight of glucosidic oligomers with degrees of polymerisation of from 2 to 10 which can be produced by the hydrolytic demolition of starches and/or dextrin with endoenzymes and the oxidation of the enzymatic hydrolytic demolition product with an oxidising agent selected from hypochlorite and periodate in association with chlorite is usable as a builder for detergents.
A mixture including oxidised glucosidic oligomers including at least 60% by weight of glucosidic oligomers with degrees of polymerisation of from 2 to 10 which can be produced by the hydrolytic demolition of starches and/or dextrin with endoenzymes and the oxidation of the enzymatic hydrolytic demolition product with an oxidising agent selected from hypochlorite and periodate in association with chlorite is usable as a builder for detergents.
Description
J ~ i.
t~ c~ p~ t~ J__ __-~ ?_-lt~ 5-P~i ~J~ ~ ~l . i i ~b~ .d~-ltt~ d th e .~ i; b u i 1 ii e r . f u r deteryent~
T,~ pri-~e~lt :in~enl;~iri reLates to c .:t :I.c.i l! Ir~-- e-luP.;terillg .s.,~.-rlt.-~ .L~ un u~.:idLie~i c-u .~ l.? ~1 `;i d !r i?. te;, t 1ll etl-lu d f u F tl-lei ~:n'f'~ lr.-lt:il!nr arlll tl-lf?:i1" I!i-i.-! -~5 hui i ~iPr s for det.eFyer,t_n Tl-le t~il:,ulyl:,l-,c,cF,I-Ic-,te Sl-PP has .c,een llsed folr m~"y ye~?l-s a, ;-.1 i I u :i l cl ~ I :i ï 1 d 1? i, e~,3e~ ir~- l? t I I i S ' I ' h;tur,l- C! i S ~ ! el.d re;Fonsi.l:!l.e ful- -tl-,e eutlcipl~,lcati~-?n o-` w.?,telr its USf' i_ C C! ntro:l:l f~ r, n: ;:! ny ~:ourltri. f` S ~-.; .-1 re.-ll:Ll; :i.nlen 7 ivl.
re;ea IrC h h-lS tal en l:,L.e~ce to id ? nilfy new bui:LdeF.~ fo~~
:i rl c:LIls:ic~ l t,, f A fol~ t:iori.-. of d etel~el.tsy to c:olTIF~:Letely c~r palrt:i.-llly rep1ace the actiurl of srPP~ hlatul~al1y~. a5 well a5 hav:in13 yoo~i caF,ahi:Lities for seql.Lesti;rin,3 calciurr arl,i mal3nesiulTl~ tl-,ese new builde Ir ~5 mll~5t al 5u be hiode,~lradahlt?.~ non--to~1.c. ani che~
In this cunnectiun, the pllb1ication in Tensiie Detel,3ent5 l4T 5 ~ 77) Of l~ Di~rrlanto.aluu et <-1]. (ref. ~1~ an,-l Gerrrli~n patent apF,lici1tion DE~ 4 r3~ 8~3 (ref. Z) pFOFIc?se tl-le u5e of .-~tarch, ce11u10sr! ar o~idatic?n Flrolluct~ and descr:il-e their se~ esteriri~3 F,FoF,eFtie~ The F.roducts obtaineli by u~:iilation with hypochlorite or peric?di?~te and suhsequent1y with cl,lorite cuntain cl-,is~in~5 with rrlany car.bo~cylic yroups ani therefoFe have hiy~, seqllestelrin~a F,nwersn The hi.,~helr tl-,e clegree of o~iiation of these sub~tis~ncc-?s, I-,uweverJ t~,e 1 owe r :is thc-?ir biodeyradahility~
t~5 stated in the F,uh].ic.?,tions of N~S. Nieuwenl-,ui~en et a1 in J~OC8, ~r 1~ 44 (1~83) (ref. ~) and 1~ ~. Crutchfield et al~ in Ji~nCS 55, 58 ~1~78) (ref~ 4) as rrloleclllaF wei~3~t decrease~5 c,io,le,3ral1ahility increases hut sel~uesterin,~
perfcrmance becurrles worse~ The puhlication reference confirrr,s th~t the biodel3r.~,iahility of polycarbc~,yl.~tes 2 ~
~ i i. n~ ? ~ . e ~ t~ rr,o:LI--cu~ r w~?i l~ ~I t;~ cl~e~c~ "ie~p].airu; ,'r,i. ~pp~ Q.I t i.,ntrc,di.ctii~n that u~i,iatic,n o.j.d~ ,i ;;tal.:l-l .5-,y ti-,i fa;:rl th..t 5hP ,~idat~,n t,.,~ P '-~ Fl ~ P
.a,-e ol~tr,ini--c5 jn ;CI~ t,iOïl re-ciuLt fron, a ch2in--delT,rilitic~-, ~.:,ri~c i.? ~
'-t.1ll:l-l. Ilowi~ ~! p ~ W O Ll ld ll.?rrl~in :int.i.cl ji.llC? it i.s ~-.ltt;lC L:: i? Cl ~ -Ir~ 1? rl,~ c~ ~ltll~ Ll l-11 I :i tc ~ tl~rl F~ f '~ I C t-.-;
slli.~w l:~ol~d ~; ~.? 1 ~ ? ':~ tel~i.rl,:~ I"~ y t 1-1 1.? ~ .? rl~t ~ Y
h:iodeyr.~c5al.lle. Io Lhi ~-an;~d pl.l.t,llcat:icn7 lt i5 indi.~ ti?d tl-,at l~ lt~ tl-iïl~ c~ ?t ~? 1 ~' bi.odi,y~ ..,c,l 1? bl.lt -~~-5~t.~ are yl~en oll their prrfornrlanre in termcj of the~ii sequeJter:iny a.5~i.1i'tie~. The reacjon iC~ e~ipresseci inT~I:Ilicitly in the introducti.on to t5-,e worL: in which it :is st.e-,teli tl~ t l:u~lyca.r~"~yl.~ted c/~nr,~ un~5s w:ith :Low mole,-~.l13l we:iyl-lt woul,l ha~e luw se,.-~llejt.e~ y po~elj-ln the course of researcl-l whi.cl-l was carried c,ut by the r~pF,:Licart c~nd led to the presrnt i~ ent:ion, :it wa~
ohser~ved that,. surF.ri~:iin,31y, on,-e the low moleclllcal weiyllt hyclrolycil; ploclui:t.; vf st.~.3.rch ~n~i cle~trin i-,~ e been o~i.dised eithe. individually or in mixtures so as to introdLIce ca.rho.~ylii yrol!F,s into tl-,eir structLIre, they s5-,ow yoo,i biodeyrada~i.lity as well as ca ,yreater eq-lesterin,3 powc?r than the F.roducts obt.~ined by tl,e o,~id~tion of starch or de~..trin~
subiect of the present in~ention is therefore the use of o,:idised ylucosidic oli,30mers wit~, deyrees of polymerisation of from 2 to 101 prefera~lly from Z to 8 and mi~tures thereof ~s blli].ders for deteryents~
The cli,~oirlers ,iefine,i aho~e inrlude pro,:lucts of the h~ cilyt:i.c l.lelTIo~.i.S~ of 't.-!ri.~ n:l~,r de~tr:in a; we:Ll a~
COiTl~ lllld ~--ui-.ln io; rr,:?l tci_e . di.lllt?1-5 ,. tt-in~erC. .i.rnrl tC-~t,I'-~ l?l'/_ .~ i Ir;~ 5 i-~ V 'li~ d, F:,f-e-t`l-f~ J.,; b C ~ . 0 'f~ :i tl: ~-r,ll o !- F~ l? f~ i O l i ?. te l f i ~-1 . 50c i. ~ i i O Tl IIJ l. tl-:I~II.:-rile ~, preFelr?i e~m~odi.lllent of tl-,e invention uses ac a ~uilder f C!l' det i-! r,-;,r.~nt- 1 rrl:ixtu f 1 j. ncludln~ t ].e.l;-t ~4 C~ t~y we:i~~lrlt, pf- er et-l A'J ly e.t Le.,.~st 7r;~, liy wejl~l-lt of 31uc,.,~_:ii:i,- c~ ,o Irler~
w:i.tl-, ~-1 /-! IJ 1' f~ F-.m~ I ~ f r:l O ~ rllC-' i" i. '.~ ~ t:iOI~ nf fr 1 rTl ~ tc 10, Fo~pfl-`l~ -y 1`1 ,r~ to f/~ WIllC h C.:-111 tJ e l~ro~!ul: ed '-,y t 11~.? i~ l'i:/L,~ tiC
,-lerl,o:L:i.t:i. f '~ If 5~ .lc:l-lP~ r ,i f-! trin w:itll . 1l,-ll.) ~-! r,~.~frl, f.?; U 1~ d tl-le f-~ tiol-i of tl-,e er,:~.yn,~tic Inydrolytic delr,olition F,ro,iuct; w:itll o~:idiiin~ ents selert?d fron, hyi:,,-":lllor:ite n,i per:io~iate in e~sC.ol-ic.~tion witln c"lorlteA T~,e n,i~ture trul~ obt.-~ ,ed ciinstitllte~s .-, furtller ~ Jject of t',-,e ple;f!nt :invf.?rlti.or ll-le o~:idation FU oress is plefela~,ly effected .L-1y sodiurr l~;ypocl-,:Loriti? wl-li-l-l is ~ eferc~llly useci w:itll~ r~tio of ~etw?en 3 and ~ mol.es of l-,ypocl-llorite pelr mole of 13J.ucosi.de units of the plod~cts ~subjected to r~inl;.~tiolln Tlle o~;i,iation re~ction :is prefelah1.y carried out with t"e FIH hetween 8 ar-,-l 10 and ~t. a terT,I:,er.,tllre of from 0 ta f'.~O~C
~nd pleff.:rabl.y f`rolT, 15 to ~O~C. Tlle metlnod of` preFIarinl t"e mimctllres mer)t:iened a~ove f c~n5titute ~ f~Urtl-ler ;ubje-t of tl-,e inventiorl as defined ir, the followin,3 claims~
T~e invent:ion will ~,e descrioed further with r~eferene to tlne followin~3 non-l:ilT,itin,3 e.~.~anTIrlles.
F~an,F,le_l~ r!ydro 1 y sis The same meth7d is used for starh and for de~trin~
.,O ~l c~ i d ~ t r i r, lLI'X; ~ i t ~? 'i t fJ ~O'~ ; f., i n .~ c c o f ~L~ 3 t. i? 1-u n ~. i 1 c o lTI I I l e t i- :l. y li i 5 5 -~ l. v ~ I ; `L~ c ~~ o f 2 i) .. ~ 1`1 1-'~ ~. 1 3 l 7 li i ~ ~ O l l l - 5 L l ! I i I i l i:: i ~ t. ~-~ t e . ~ I 1 11 t. :i ~; o w I ~ i F~ l 1 t IJ t I I F ~ L ll t .i. o ri . r " i-!
1 2 '~ t i i ) ~ . t. I ~ i -f F ~ ~1 t :~ I L' r.. I 1-t I, iA rl .-., rl i! ~ 1 .. T 1-1 f ~ 111 1 ; t ll i P ~A~ : ¦ f A F t t ,~ F P .-i i t ~ f l! U i I I O ~
t~ c~ p~ t~ J__ __-~ ?_-lt~ 5-P~i ~J~ ~ ~l . i i ~b~ .d~-ltt~ d th e .~ i; b u i 1 ii e r . f u r deteryent~
T,~ pri-~e~lt :in~enl;~iri reLates to c .:t :I.c.i l! Ir~-- e-luP.;terillg .s.,~.-rlt.-~ .L~ un u~.:idLie~i c-u .~ l.? ~1 `;i d !r i?. te;, t 1ll etl-lu d f u F tl-lei ~:n'f'~ lr.-lt:il!nr arlll tl-lf?:i1" I!i-i.-! -~5 hui i ~iPr s for det.eFyer,t_n Tl-le t~il:,ulyl:,l-,c,cF,I-Ic-,te Sl-PP has .c,een llsed folr m~"y ye~?l-s a, ;-.1 i I u :i l cl ~ I :i ï 1 d 1? i, e~,3e~ ir~- l? t I I i S ' I ' h;tur,l- C! i S ~ ! el.d re;Fonsi.l:!l.e ful- -tl-,e eutlcipl~,lcati~-?n o-` w.?,telr its USf' i_ C C! ntro:l:l f~ r, n: ;:! ny ~:ourltri. f` S ~-.; .-1 re.-ll:Ll; :i.nlen 7 ivl.
re;ea IrC h h-lS tal en l:,L.e~ce to id ? nilfy new bui:LdeF.~ fo~~
:i rl c:LIls:ic~ l t,, f A fol~ t:iori.-. of d etel~el.tsy to c:olTIF~:Letely c~r palrt:i.-llly rep1ace the actiurl of srPP~ hlatul~al1y~. a5 well a5 hav:in13 yoo~i caF,ahi:Lities for seql.Lesti;rin,3 calciurr arl,i mal3nesiulTl~ tl-,ese new builde Ir ~5 mll~5t al 5u be hiode,~lradahlt?.~ non--to~1.c. ani che~
In this cunnectiun, the pllb1ication in Tensiie Detel,3ent5 l4T 5 ~ 77) Of l~ Di~rrlanto.aluu et <-1]. (ref. ~1~ an,-l Gerrrli~n patent apF,lici1tion DE~ 4 r3~ 8~3 (ref. Z) pFOFIc?se tl-le u5e of .-~tarch, ce11u10sr! ar o~idatic?n Flrolluct~ and descr:il-e their se~ esteriri~3 F,FoF,eFtie~ The F.roducts obtaineli by u~:iilation with hypochlorite or peric?di?~te and suhsequent1y with cl,lorite cuntain cl-,is~in~5 with rrlany car.bo~cylic yroups ani therefoFe have hiy~, seqllestelrin~a F,nwersn The hi.,~helr tl-,e clegree of o~iiation of these sub~tis~ncc-?s, I-,uweverJ t~,e 1 owe r :is thc-?ir biodeyradahility~
t~5 stated in the F,uh].ic.?,tions of N~S. Nieuwenl-,ui~en et a1 in J~OC8, ~r 1~ 44 (1~83) (ref. ~) and 1~ ~. Crutchfield et al~ in Ji~nCS 55, 58 ~1~78) (ref~ 4) as rrloleclllaF wei~3~t decrease~5 c,io,le,3ral1ahility increases hut sel~uesterin,~
perfcrmance becurrles worse~ The puhlication reference confirrr,s th~t the biodel3r.~,iahility of polycarbc~,yl.~tes 2 ~
~ i i. n~ ? ~ . e ~ t~ rr,o:LI--cu~ r w~?i l~ ~I t;~ cl~e~c~ "ie~p].airu; ,'r,i. ~pp~ Q.I t i.,ntrc,di.ctii~n that u~i,iatic,n o.j.d~ ,i ;;tal.:l-l .5-,y ti-,i fa;:rl th..t 5hP ,~idat~,n t,.,~ P '-~ Fl ~ P
.a,-e ol~tr,ini--c5 jn ;CI~ t,iOïl re-ciuLt fron, a ch2in--delT,rilitic~-, ~.:,ri~c i.? ~
'-t.1ll:l-l. Ilowi~ ~! p ~ W O Ll ld ll.?rrl~in :int.i.cl ji.llC? it i.s ~-.ltt;lC L:: i? Cl ~ -Ir~ 1? rl,~ c~ ~ltll~ Ll l-11 I :i tc ~ tl~rl F~ f '~ I C t-.-;
slli.~w l:~ol~d ~; ~.? 1 ~ ? ':~ tel~i.rl,:~ I"~ y t 1-1 1.? ~ .? rl~t ~ Y
h:iodeyr.~c5al.lle. Io Lhi ~-an;~d pl.l.t,llcat:icn7 lt i5 indi.~ ti?d tl-,at l~ lt~ tl-iïl~ c~ ?t ~? 1 ~' bi.odi,y~ ..,c,l 1? bl.lt -~~-5~t.~ are yl~en oll their prrfornrlanre in termcj of the~ii sequeJter:iny a.5~i.1i'tie~. The reacjon iC~ e~ipresseci inT~I:Ilicitly in the introducti.on to t5-,e worL: in which it :is st.e-,teli tl~ t l:u~lyca.r~"~yl.~ted c/~nr,~ un~5s w:ith :Low mole,-~.l13l we:iyl-lt woul,l ha~e luw se,.-~llejt.e~ y po~elj-ln the course of researcl-l whi.cl-l was carried c,ut by the r~pF,:Licart c~nd led to the presrnt i~ ent:ion, :it wa~
ohser~ved that,. surF.ri~:iin,31y, on,-e the low moleclllcal weiyllt hyclrolycil; ploclui:t.; vf st.~.3.rch ~n~i cle~trin i-,~ e been o~i.dised eithe. individually or in mixtures so as to introdLIce ca.rho.~ylii yrol!F,s into tl-,eir structLIre, they s5-,ow yoo,i biodeyrada~i.lity as well as ca ,yreater eq-lesterin,3 powc?r than the F.roducts obt.~ined by tl,e o,~id~tion of starch or de~..trin~
subiect of the present in~ention is therefore the use of o,:idised ylucosidic oli,30mers wit~, deyrees of polymerisation of from 2 to 101 prefera~lly from Z to 8 and mi~tures thereof ~s blli].ders for deteryents~
The cli,~oirlers ,iefine,i aho~e inrlude pro,:lucts of the h~ cilyt:i.c l.lelTIo~.i.S~ of 't.-!ri.~ n:l~,r de~tr:in a; we:Ll a~
COiTl~ lllld ~--ui-.ln io; rr,:?l tci_e . di.lllt?1-5 ,. tt-in~erC. .i.rnrl tC-~t,I'-~ l?l'/_ .~ i Ir;~ 5 i-~ V 'li~ d, F:,f-e-t`l-f~ J.,; b C ~ . 0 'f~ :i tl: ~-r,ll o !- F~ l? f~ i O l i ?. te l f i ~-1 . 50c i. ~ i i O Tl IIJ l. tl-:I~II.:-rile ~, preFelr?i e~m~odi.lllent of tl-,e invention uses ac a ~uilder f C!l' det i-! r,-;,r.~nt- 1 rrl:ixtu f 1 j. ncludln~ t ].e.l;-t ~4 C~ t~y we:i~~lrlt, pf- er et-l A'J ly e.t Le.,.~st 7r;~, liy wejl~l-lt of 31uc,.,~_:ii:i,- c~ ,o Irler~
w:i.tl-, ~-1 /-! IJ 1' f~ F-.m~ I ~ f r:l O ~ rllC-' i" i. '.~ ~ t:iOI~ nf fr 1 rTl ~ tc 10, Fo~pfl-`l~ -y 1`1 ,r~ to f/~ WIllC h C.:-111 tJ e l~ro~!ul: ed '-,y t 11~.? i~ l'i:/L,~ tiC
,-lerl,o:L:i.t:i. f '~ If 5~ .lc:l-lP~ r ,i f-! trin w:itll . 1l,-ll.) ~-! r,~.~frl, f.?; U 1~ d tl-le f-~ tiol-i of tl-,e er,:~.yn,~tic Inydrolytic delr,olition F,ro,iuct; w:itll o~:idiiin~ ents selert?d fron, hyi:,,-":lllor:ite n,i per:io~iate in e~sC.ol-ic.~tion witln c"lorlteA T~,e n,i~ture trul~ obt.-~ ,ed ciinstitllte~s .-, furtller ~ Jject of t',-,e ple;f!nt :invf.?rlti.or ll-le o~:idation FU oress is plefela~,ly effected .L-1y sodiurr l~;ypocl-,:Loriti? wl-li-l-l is ~ eferc~llly useci w:itll~ r~tio of ~etw?en 3 and ~ mol.es of l-,ypocl-llorite pelr mole of 13J.ucosi.de units of the plod~cts ~subjected to r~inl;.~tiolln Tlle o~;i,iation re~ction :is prefelah1.y carried out with t"e FIH hetween 8 ar-,-l 10 and ~t. a terT,I:,er.,tllre of from 0 ta f'.~O~C
~nd pleff.:rabl.y f`rolT, 15 to ~O~C. Tlle metlnod of` preFIarinl t"e mimctllres mer)t:iened a~ove f c~n5titute ~ f~Urtl-ler ;ubje-t of tl-,e inventiorl as defined ir, the followin,3 claims~
T~e invent:ion will ~,e descrioed further with r~eferene to tlne followin~3 non-l:ilT,itin,3 e.~.~anTIrlles.
F~an,F,le_l~ r!ydro 1 y sis The same meth7d is used for starh and for de~trin~
.,O ~l c~ i d ~ t r i r, lLI'X; ~ i t ~? 'i t fJ ~O'~ ; f., i n .~ c c o f ~L~ 3 t. i? 1-u n ~. i 1 c o lTI I I l e t i- :l. y li i 5 5 -~ l. v ~ I ; `L~ c ~~ o f 2 i) .. ~ 1`1 1-'~ ~. 1 3 l 7 li i ~ ~ O l l l - 5 L l ! I i I i l i:: i ~ t. ~-~ t e . ~ I 1 11 t. :i ~; o w I ~ i F~ l 1 t IJ t I I F ~ L ll t .i. o ri . r " i-!
1 2 '~ t i i ) ~ . t. I ~ i -f F ~ ~1 t :~ I L' r.. I 1-t I, iA rl .-., rl i! ~ 1 .. T 1-1 f ~ 111 1 ; t ll i P ~A~ : ¦ f A F t t ,~ F P .-i i t ~ f l! U i I I O ~
-3 t 4_ ~. d I i d t 17 1 ` rl L r l t i.-. t . ` I TI ~ il t t F? ITI F- e 1- c; i. u !~ L:' f riU~ i O 17 o u 1~ 5 .
F~ l F~ ]. f3 _.'. . _ 1 ~ t.i ~ .r.~.. .'L-' _ t.~ - -] l.~
o f c 3 r ~ 3 t i w ., '3 d i s ~- o ~. v c~ d o 1- =. u - F~ c -r, ii ~? i A i rl ' ~ 5 c c u f ~ le1~, 10 ~ c ~J ,` ~ m h Fl~:: h :L,"-il. ~? . f! L 1.1i;:i,f.' r, 17 t 3 i " i ri ~ 1 .3 i~ .. , y ~1 c- i IJ I 7 t O -r c 1, :L O ~ L' W ~ l i. e ¦ t I I l? Fl 11 W 3 ~ n-l j 1 , .- t -: -l t o LC.~ w i. t , l c ~ i l r i- l i t ,- .-.3 t ~. ~-J 1 , y c! 1~ u c 1-1 :L C! 1' :i C .0 i: :i d ~ .
t h :i-i~ pl-i v .~1 u e w~, rm.l1r, t e.i n Qli d u in1~ 5 U C r i?5~siY e i~ d dition~
O j! , i, F~ o c ~ , i. t i~ :, t o .-i t r o t. ~ 1 1 o f 2 o ro--~ 0 0 c i 1_! i i t " f~ h ~
o j! t I I f A i n i t i ~ ]. 5 t r e n ,~ t I, 5 o t I, 3 t t I ".- ~ F~ a ~ 3 t :i. f l O F ~3--*
o l P 5 o f f'l ~ 1~ O c 17 I o ~ :i t P ~:1 e 1 ITI O L e .-:, f .:1 :1. u i- i! :~ C' 1117 i t ~- .
~, f t e r t h e e.i d i.t:ion o t' t h ~ h YF~oc h lo r ite r t~,e pl-i w~ 5 k: 'p t col7~;te.nt by the ~irl:it:ion Or` -Onf entfi.3~ted Nii~7~H~ Tl-le temper2iure w~5 I:c3FIt e~,t 15-20C. The te~t w~3~ stopF~ed when tl-~e resi:lu~-~l chlorine l:,ec~-lnle ne,~ :lr.-!. The rec.~.ct:ion time v.-1riell with tl-,e tyFIe ot` ~u.h~.;tri~te hl.lt the solution w--~ ir, c3~ny c~-~-.e left .~lone for 24 hou~ the tc-~rr,pe~l~tllre ~till bei.nl3 k:eF,t ~.t ',5-Z0C. The o~ idi~ed ~.~mple w-.,~ seF,<---ri~ted l-JY .iouble precipit~t:ion with ;-~lcohol in the ca~e of ~t~e.Fch or de~trin, or c.y e~pori.-,.tiol7 in ~ rot3v3pol in uther c~?~se~;. The ~rr,F,le~ w:ith low nlolecu]~r wei~3hts c.ln al~o be precipit3te:1 with ~lcol~,ol l-~ut wit~, very limitei yields.
N~,tur~lly, when the ~;epalrat:iorl is effectei by elt..-.ipor~tion ~ a consi,ie~2ble ,l,u~ntity of ~odium chloride i~ pre~ent but t~,is h~5 little effect on the test~ of t~,e ~e~lue~,tfin~
powe r 2nd ~i ode~ r 2 i~bi 1 i ty .
.p I ~ t.i c. r~ .F, - ., i o~ t e ~ d ~ 1 c i.r, t,',i. ~:a5~ i;3 i1 oi sT~ ch o~- dent~-ir~ W=5 uiei~ Fol f.. , ' / i. ITI ~ ' 5 U ~ F ~- i, cl e ~ I C ~ . f ! ~3 t e I ~ f I .:1 C~ t o i c I, i o I I, e t Ir 1. C
ql.l2rltit~ o,` sc.di.ulTI pel-:icida-te ~30 ,~i ci:issclvfd :in 4~Ci rc wi ~ 5 ii c~ t, e F~'-l w ~ F: t i-~ t i . , I-l e ITI l `' t u ~ ~ w ~ 5 1 e f t t o r ee~ t a-t l5-20~ in tl,e d~e.~: foi~ 2', houl 5 and the f?FiO ci..-~t l? ,-: o ~t f~ r t o F ~ " (:! c; o :L u t:i o n w.-~ 5 i.~,en c l, F~ c1 ell. Tl-l~?
iie.-i:Lll e hycle W;3S p ~ 0 ~ : e,! .-,nd :i t-i F~ I~ ec~ :i t a.ti., n W.-.-~`.;
fe~c:i:L j.tate(l t?y ..-~.I-n-ii~lcil nlr .*cetone.. The pl-"c:iplt.-~te waC
W :.-1'. i I 1 1? 1~ i t l-l ? :L c: I! i-, c, L o I ~-, c i? t o r, (:! 2 i~ ll d i :i ~-- d . -l r, ~J r C' F t f , :i t l-l ~
l,eer, ~ e :i13 hed r a rl ~3 SPSFS84-~ --! mp :L e w-~ p 1 a ce~i :in Z.~0 c c o ~ -a ~; o :L ut i i~ n t.. -l :i n 1. n ~ ~c~ o f S l:, cl i UiT~ C h ]. -i 1 ] t e y t o w 11 i C i'l ~'J. 5 cc c,F ~ c:iial ai:et~c ac:id we ~-e added .-lowly. r"e IT~ tUi'e W:~5 left at 15-20C fof 2', hl-iu~ n~i w~ il-,e..i ln a f:l.ow of nitl o,3en to l emo~ e tl,e Iremair)in~3 chloi i.t...
Pl ec:il:,it2t:ion w.~ ef,`ected with 2: 1 alcollol arlci watet . Tlle p~ olluct oJ:ta:ined wa~i dirieci in o~:le~ to det.errrline it cieq~le~terin,~ powe,~ an-i Fo, t,',e biucie.3iradat~ility test.
E._i ~mF~1e ~ Detc!rm~r_aticjn _c~F t,', e,_s e~u f.~ te, in~_p~we ~
The r; c~ql.lecite~ powel (pS) ii noi~ mally e~iF~ ir e~se~i in rTI.~ o,`
c?lc:iurTI cairbonate pe~ m of seqlleste,~in,~ a.,~ent .~ncL can l:e ~letel rnined ~y the tit~ tion of the sequesteirinl~ 2,~ent wit,', a solution of a c.alciurT, salt~ ,~ pctentiorrleti~ic electrode wit,', a rr,em~:irane w~s used to dete~rr,ine the e,~uivalence point~ T,he tit~tion was stc!F.F.ed when the calcium ion concent,~ation was 0~0005 moles~litire w,',ich is the soluc,ility of t,',e c~lcium ion in the ca,r~onate~
~lte,rnativelyr the effect of the ad,iition of a solution of the sequestei~in,~ a~3ent to c~ solution of cal ciurr, r ontaininl3~ fol~ e~amF~le~ O.G025 moles~litire of calcium ( 14~ Ge~ m~n ,'~ardnecis) was investi~3ated~ The dec,rease in the l,a~dness of t,',e w~te~r ~5 a ,~esult of the successive 2 ~ iY ~;, ;..,r!ditloni of ~e,-luP5-t i? I' :i r~ ! nt ~ follow,~,1 w i ti-, tl, i?
F,otentl2ll,e-tl-lc eLe~odi. Tn1.~; l.ette r mctl-,od l~ -the r~t.-l,.-~ f .-~ 3 :illlll,e~ te:l, tr~ 7ltit.y ~ ` t,,~
e-~ r, (-~ 7~ ee,iel.i .2 ~ 1? tl-lP de~ d 1: .?. L ~: i UIT
~ e:l in t.i-,e W.lti?l.
Fiiodl-l3i;-,Ll;~b:il:ity _ st--In tl-le fo:l lowinl~ ei~rlll:ll.i;, the rP.-.~dy bjorl~ a~ .il:ity of tl-,e pFurlucts l~bti~ined w-l5 ir,~estilJ~?tl?d by tl-le cl.ored---buttLe te.-it ~ b~ lt.l in the Qi`fic.ii.-~ .a;: tt.e o f ~h~
Eul-,3l:lean ~orrllr~ 1.! n i. t, y L .'~ t:ion7 Ite.i:i-i.n kn~ r-edition~ th cj 1.? Flterr,l.,l.~r 1~2'i.
1,-, `., cl, rr.!.F~ l e 5 Tl-,e en;~ylli~tic hydirolyciis n,eti~"3d de--i,-ribed ir)~ n,F~le 1 wi3s aF,F,l:iell t~3 de:~tlrin of tl-le 5nowfla~e 1'~11 type. IJF,on i-lPI.C
analysisy it w~s found that this rie:~trin ront~ined 14~ ~y we:i,3ht of oliyonTIers witl-, le-is than 7 ,Jlu~:,3;ide unit.s. The di;tlributioll withi.n ti~~is fr~rtion W~5 a5 foll,3ws Lucoside units l 2 3 4 5 6 7 .",' by wei.,3ht 2.5 l1..6 lq.6 16~4 lP~4 ~6~ 5rZ
After hydrolysisr the same dce:trin hc~d 77~ b~ wei,3ht of ol:igorr~ers with le55 than 7 ~31uco-iide unit~;. The distriblltion within this f~c~ction w~s as follows:
~31ucoside units l 2 3 4 5 6 7 % by weil3ht 11 Z2~4 24~4 10~4 ~6.0 4~0 1.7 5 y of de~trin hydrolyse~ .~s described ~bo~e w~s o~idi~ed with so,iiurr, hyporhlorite ac~r~iin~3 to t~,e nr,ethod desrFit,ed in E~arr,ple 2, the ratio of hypochlorite/,~lucoside ~nits i~3~ iiV~
cil~3 I:r-F:!t .. ~ ftc~l o `' ~ .l t :i or), F:~ F ~ C i Flit`~ t i o n w i i. I-1. y:i.~:L!~ IT) t l-l e :i n l t i j~ :L r~ 3 ~ t I I ,~
t ~ r~ "J ~ C ~} . 1-l-l e P~ c~ i~ " 1'le 1~ .. t :~
r ~-l h . ~ F .~ ffo~ Tll~ F~l o~ t ~J~-!.-.t.~ 3~ ,l e :i ri e~ 51? ~r~;7~ f-te~ `f'~ i t.1-1f-~
.-: :L ~ L e l e -~ t !
E~-~r"F,le ::
_.__ ____ _ o r 11 i -l L t ~ t ! I O ~ .,IJ . ~ ,, O "'. i. il i S ~ ,lj i t, I , I f p C1 ~ . Ci ! i t e .LI j t I I ,-~
n;et ilud ~le ~:r :i l! e d ~ o E. -~ Lc 2 ti-ie r ~ t:i ~/ 01'` I-ly;,.:,~-:l-ll. i :i t,l.
.3 :lu~ s:ide ur,:i.t . .te :irilJ Fn~ r~ t ~t 5. T he fin-~:l. ;olllt lor, w.~s l ,1 i? .-l il~t:o two F,:F t ~.~r,~l .on r-! F~-~r t W.li Fn r ~? r: i. F:i t -~ t e ~! W :i t, I
cl-~ nd t,'len filtelred F~Fodiucin,3 1..5 l~ of tl-,e F~Fc.duct fFO m ~i.i-le init:i.~l 5 ~r"-l t ~lr-! ot hc f wcls eY~e~F~olri~ted to d i"y ne,s. Iri t 1-1 f5 L;~.tt eF C ase t 1-1 e F~ F e lirrlina Fy Ci ete lrmin ~t :i on of th e c ll:Lc~ rides eni-~ t.].Pd its cor Ir ect, se o, uee~ t e rin.3 p~er tci be d et e Ir rmin ecl.. rl-le P 5 ''f'-~lU e oht~inec', w~s ~ in tl-l e fi IrS t c~se ~nd ;?0(~ in tt~e second. T,-,e bic)de.-!F~ .t/ility ~ ? tlle FiFCidU~:t W~3S veFy ~ood in e.~c,~ c~se ~ fter 28 clhys in the clo~.-.ec'~ ottle test)~
E ~mF~l e 7 /
5 " c~f rrl.-,ltose W~35 oxidised witl-l "yF,c,c"loFite by the rr,ethod deecribed in E}~.~rr,p:Le ~ n Two s~rr,F,les welre F~lrociuced~
one .O\f F,Fecipitation ~ t`Fom 5) and one by ev~.F,or-~tirin..
T,le PS W.-i5 ~20 f!~ the first s~rrlple ~nd 340 for- t,le second. T,~le pFociuct w~s Fe~dily hiode~r~d~ble in e~c,'~ c~se ~ % ~fteF 25 d~ys in t"e closed-~lottle test).
En~.rr~F 5 (Corr,F,~F~ti~e) Con,F.~.r~ti~e tests were c~.FFied L~Ut ~iy t,~,e o~ici~tion of 2~Y~i3 .;t.~r~ r~ -;r~liw~ qll dP~t~ y t,f~ rr,etl~ l de5~ d :in E~ r,~ Z arl d wi th ~5~ t-C~t il~ 0 f 5 nlo li?S O f ~ Li~r.i~ loLe i~ f l I L ~! C ~ i c~ l i. t. _ n fJ :i. tl-l rl-lf-~ u~ -- t d 1" i~ b o u t, ~ u ~ i d i ~- e li c t ~5.lcl-l w~
~ t ~ , e ~ d ,f~ c-~ lfiti~r:ir~l~ F~ C~ w e r , ~ ~ ~s~l!c~llt Z~J~i. -r ~l l?
prudllct was nL~i very biode~3l-aci.a~LL3 (~i~ dftelr Z~i d.5.ys in t h e ~ .l --hc! t t ] e tPSt)n In thl~ c~e uf cli ~tlri n wi th sep?l atiu71 c.~l-r ~ d uut :in the ~ a In e n ~ a 1 ~ n i? r, S' . ~ C1 1` 0 ~ :i cl :i 5 e d F:~ r o d u c t w ~ s F e r o v e r e d .e.r~
h ~d a s e quf~stLs t-i rl~3 puw 1.? r o f ~5. rl-, e p t- O d uc t ~I-u~w e d pu c~ r 1:! i. o cl ~? ~ lcl~5.~i :i :l ity (: ~: I X ;n .?~ f tf~ r c~ ~i cl .~ ~ ; :i rl t ~, e c ]. ci ~ d ---1 ! O t t l L
t e 5 t ! A
Tl-le st.:slrches used in tl-le pr'esent invellttion ~5~1~e prefet-abLy ~;tat-cl-lfn-~ ` ns~tur-c~l vel~et2ble C!rlyin r,~rr,pu5ed e~enti-llly of a~ylcise and 3rnyloFIectin~
rr~ r~ q }etelrl3Qnt COIllFlOsitiOns wet-e preFi~reci wi th the use of the proc1uct of E~anrlF,le 5 as o~tained hy direct eve.F,ir~ratiun without preciFIit~a~tion with ~lcu~lol.
The cleteryent curnpclsition w~s as follows:
Euilder- (E~n 5i100 part~ wt L~s (linear alF~yl SlllpihQnate.) Soap Non ioni c surfactant HT 1 'l 5 Tetraper borate (~leachin,~ a,3enti ~isilic~-5te Cat borlate 10 2 ~
Tlle c.lc~ e cc!rr,~ -.i.tion ~ tested :in ~-e-,pert r,f it, :ntl~-YIleFlo~iti.on -~.nd :~o~ rmr/.~l effel-.t ~.n,.l ~1ol~)eli 1 i ;a i.l ]. t; 5 .~ 1 1 t ~1 t. 1 1 0 i~ f ~ P r) t. ~ t .~ c. T I t. i i n 1 1. 1.1 li i. n ~-1 t, ~ ~ . n~ o -1' f` e .: t :i .. ~ e ~-, In o l.l n t o f t l-l c~ 0 ~J l_ .:,G I-le l t ~ d i. n ~ r:~ l Fl~ t ~ ~, n,-l ~ y l i r r i. cl .' m.~ :L e i ~ 5 t 1-1 e c- -f -f` e; t, :i ~f' ~e h l.l i 1 cl e lr ~
'' ''
F~ l F~ ]. f3 _.'. . _ 1 ~ t.i ~ .r.~.. .'L-' _ t.~ - -] l.~
o f c 3 r ~ 3 t i w ., '3 d i s ~- o ~. v c~ d o 1- =. u - F~ c -r, ii ~? i A i rl ' ~ 5 c c u f ~ le1~, 10 ~ c ~J ,` ~ m h Fl~:: h :L,"-il. ~? . f! L 1.1i;:i,f.' r, 17 t 3 i " i ri ~ 1 .3 i~ .. , y ~1 c- i IJ I 7 t O -r c 1, :L O ~ L' W ~ l i. e ¦ t I I l? Fl 11 W 3 ~ n-l j 1 , .- t -: -l t o LC.~ w i. t , l c ~ i l r i- l i t ,- .-.3 t ~. ~-J 1 , y c! 1~ u c 1-1 :L C! 1' :i C .0 i: :i d ~ .
t h :i-i~ pl-i v .~1 u e w~, rm.l1r, t e.i n Qli d u in1~ 5 U C r i?5~siY e i~ d dition~
O j! , i, F~ o c ~ , i. t i~ :, t o .-i t r o t. ~ 1 1 o f 2 o ro--~ 0 0 c i 1_! i i t " f~ h ~
o j! t I I f A i n i t i ~ ]. 5 t r e n ,~ t I, 5 o t I, 3 t t I ".- ~ F~ a ~ 3 t :i. f l O F ~3--*
o l P 5 o f f'l ~ 1~ O c 17 I o ~ :i t P ~:1 e 1 ITI O L e .-:, f .:1 :1. u i- i! :~ C' 1117 i t ~- .
~, f t e r t h e e.i d i.t:ion o t' t h ~ h YF~oc h lo r ite r t~,e pl-i w~ 5 k: 'p t col7~;te.nt by the ~irl:it:ion Or` -Onf entfi.3~ted Nii~7~H~ Tl-le temper2iure w~5 I:c3FIt e~,t 15-20C. The te~t w~3~ stopF~ed when tl-~e resi:lu~-~l chlorine l:,ec~-lnle ne,~ :lr.-!. The rec.~.ct:ion time v.-1riell with tl-,e tyFIe ot` ~u.h~.;tri~te hl.lt the solution w--~ ir, c3~ny c~-~-.e left .~lone for 24 hou~ the tc-~rr,pe~l~tllre ~till bei.nl3 k:eF,t ~.t ',5-Z0C. The o~ idi~ed ~.~mple w-.,~ seF,<---ri~ted l-JY .iouble precipit~t:ion with ;-~lcohol in the ca~e of ~t~e.Fch or de~trin, or c.y e~pori.-,.tiol7 in ~ rot3v3pol in uther c~?~se~;. The ~rr,F,le~ w:ith low nlolecu]~r wei~3hts c.ln al~o be precipit3te:1 with ~lcol~,ol l-~ut wit~, very limitei yields.
N~,tur~lly, when the ~;epalrat:iorl is effectei by elt..-.ipor~tion ~ a consi,ie~2ble ,l,u~ntity of ~odium chloride i~ pre~ent but t~,is h~5 little effect on the test~ of t~,e ~e~lue~,tfin~
powe r 2nd ~i ode~ r 2 i~bi 1 i ty .
.p I ~ t.i c. r~ .F, - ., i o~ t e ~ d ~ 1 c i.r, t,',i. ~:a5~ i;3 i1 oi sT~ ch o~- dent~-ir~ W=5 uiei~ Fol f.. , ' / i. ITI ~ ' 5 U ~ F ~- i, cl e ~ I C ~ . f ! ~3 t e I ~ f I .:1 C~ t o i c I, i o I I, e t Ir 1. C
ql.l2rltit~ o,` sc.di.ulTI pel-:icida-te ~30 ,~i ci:issclvfd :in 4~Ci rc wi ~ 5 ii c~ t, e F~'-l w ~ F: t i-~ t i . , I-l e ITI l `' t u ~ ~ w ~ 5 1 e f t t o r ee~ t a-t l5-20~ in tl,e d~e.~: foi~ 2', houl 5 and the f?FiO ci..-~t l? ,-: o ~t f~ r t o F ~ " (:! c; o :L u t:i o n w.-~ 5 i.~,en c l, F~ c1 ell. Tl-l~?
iie.-i:Lll e hycle W;3S p ~ 0 ~ : e,! .-,nd :i t-i F~ I~ ec~ :i t a.ti., n W.-.-~`.;
fe~c:i:L j.tate(l t?y ..-~.I-n-ii~lcil nlr .*cetone.. The pl-"c:iplt.-~te waC
W :.-1'. i I 1 1? 1~ i t l-l ? :L c: I! i-, c, L o I ~-, c i? t o r, (:! 2 i~ ll d i :i ~-- d . -l r, ~J r C' F t f , :i t l-l ~
l,eer, ~ e :i13 hed r a rl ~3 SPSFS84-~ --! mp :L e w-~ p 1 a ce~i :in Z.~0 c c o ~ -a ~; o :L ut i i~ n t.. -l :i n 1. n ~ ~c~ o f S l:, cl i UiT~ C h ]. -i 1 ] t e y t o w 11 i C i'l ~'J. 5 cc c,F ~ c:iial ai:et~c ac:id we ~-e added .-lowly. r"e IT~ tUi'e W:~5 left at 15-20C fof 2', hl-iu~ n~i w~ il-,e..i ln a f:l.ow of nitl o,3en to l emo~ e tl,e Iremair)in~3 chloi i.t...
Pl ec:il:,it2t:ion w.~ ef,`ected with 2: 1 alcollol arlci watet . Tlle p~ olluct oJ:ta:ined wa~i dirieci in o~:le~ to det.errrline it cieq~le~terin,~ powe,~ an-i Fo, t,',e biucie.3iradat~ility test.
E._i ~mF~1e ~ Detc!rm~r_aticjn _c~F t,', e,_s e~u f.~ te, in~_p~we ~
The r; c~ql.lecite~ powel (pS) ii noi~ mally e~iF~ ir e~se~i in rTI.~ o,`
c?lc:iurTI cairbonate pe~ m of seqlleste,~in,~ a.,~ent .~ncL can l:e ~letel rnined ~y the tit~ tion of the sequesteirinl~ 2,~ent wit,', a solution of a c.alciurT, salt~ ,~ pctentiorrleti~ic electrode wit,', a rr,em~:irane w~s used to dete~rr,ine the e,~uivalence point~ T,he tit~tion was stc!F.F.ed when the calcium ion concent,~ation was 0~0005 moles~litire w,',ich is the soluc,ility of t,',e c~lcium ion in the ca,r~onate~
~lte,rnativelyr the effect of the ad,iition of a solution of the sequestei~in,~ a~3ent to c~ solution of cal ciurr, r ontaininl3~ fol~ e~amF~le~ O.G025 moles~litire of calcium ( 14~ Ge~ m~n ,'~ardnecis) was investi~3ated~ The dec,rease in the l,a~dness of t,',e w~te~r ~5 a ,~esult of the successive 2 ~ iY ~;, ;..,r!ditloni of ~e,-luP5-t i? I' :i r~ ! nt ~ follow,~,1 w i ti-, tl, i?
F,otentl2ll,e-tl-lc eLe~odi. Tn1.~; l.ette r mctl-,od l~ -the r~t.-l,.-~ f .-~ 3 :illlll,e~ te:l, tr~ 7ltit.y ~ ` t,,~
e-~ r, (-~ 7~ ee,iel.i .2 ~ 1? tl-lP de~ d 1: .?. L ~: i UIT
~ e:l in t.i-,e W.lti?l.
Fiiodl-l3i;-,Ll;~b:il:ity _ st--In tl-le fo:l lowinl~ ei~rlll:ll.i;, the rP.-.~dy bjorl~ a~ .il:ity of tl-,e pFurlucts l~bti~ined w-l5 ir,~estilJ~?tl?d by tl-le cl.ored---buttLe te.-it ~ b~ lt.l in the Qi`fic.ii.-~ .a;: tt.e o f ~h~
Eul-,3l:lean ~orrllr~ 1.! n i. t, y L .'~ t:ion7 Ite.i:i-i.n kn~ r-edition~ th cj 1.? Flterr,l.,l.~r 1~2'i.
1,-, `., cl, rr.!.F~ l e 5 Tl-,e en;~ylli~tic hydirolyciis n,eti~"3d de--i,-ribed ir)~ n,F~le 1 wi3s aF,F,l:iell t~3 de:~tlrin of tl-le 5nowfla~e 1'~11 type. IJF,on i-lPI.C
analysisy it w~s found that this rie:~trin ront~ined 14~ ~y we:i,3ht of oliyonTIers witl-, le-is than 7 ,Jlu~:,3;ide unit.s. The di;tlributioll withi.n ti~~is fr~rtion W~5 a5 foll,3ws Lucoside units l 2 3 4 5 6 7 .",' by wei.,3ht 2.5 l1..6 lq.6 16~4 lP~4 ~6~ 5rZ
After hydrolysisr the same dce:trin hc~d 77~ b~ wei,3ht of ol:igorr~ers with le55 than 7 ~31uco-iide unit~;. The distriblltion within this f~c~ction w~s as follows:
~31ucoside units l 2 3 4 5 6 7 % by weil3ht 11 Z2~4 24~4 10~4 ~6.0 4~0 1.7 5 y of de~trin hydrolyse~ .~s described ~bo~e w~s o~idi~ed with so,iiurr, hyporhlorite ac~r~iin~3 to t~,e nr,ethod desrFit,ed in E~arr,ple 2, the ratio of hypochlorite/,~lucoside ~nits i~3~ iiV~
cil~3 I:r-F:!t .. ~ ftc~l o `' ~ .l t :i or), F:~ F ~ C i Flit`~ t i o n w i i. I-1. y:i.~:L!~ IT) t l-l e :i n l t i j~ :L r~ 3 ~ t I I ,~
t ~ r~ "J ~ C ~} . 1-l-l e P~ c~ i~ " 1'le 1~ .. t :~
r ~-l h . ~ F .~ ffo~ Tll~ F~l o~ t ~J~-!.-.t.~ 3~ ,l e :i ri e~ 51? ~r~;7~ f-te~ `f'~ i t.1-1f-~
.-: :L ~ L e l e -~ t !
E~-~r"F,le ::
_.__ ____ _ o r 11 i -l L t ~ t ! I O ~ .,IJ . ~ ,, O "'. i. il i S ~ ,lj i t, I , I f p C1 ~ . Ci ! i t e .LI j t I I ,-~
n;et ilud ~le ~:r :i l! e d ~ o E. -~ Lc 2 ti-ie r ~ t:i ~/ 01'` I-ly;,.:,~-:l-ll. i :i t,l.
.3 :lu~ s:ide ur,:i.t . .te :irilJ Fn~ r~ t ~t 5. T he fin-~:l. ;olllt lor, w.~s l ,1 i? .-l il~t:o two F,:F t ~.~r,~l .on r-! F~-~r t W.li Fn r ~? r: i. F:i t -~ t e ~! W :i t, I
cl-~ nd t,'len filtelred F~Fodiucin,3 1..5 l~ of tl-,e F~Fc.duct fFO m ~i.i-le init:i.~l 5 ~r"-l t ~lr-! ot hc f wcls eY~e~F~olri~ted to d i"y ne,s. Iri t 1-1 f5 L;~.tt eF C ase t 1-1 e F~ F e lirrlina Fy Ci ete lrmin ~t :i on of th e c ll:Lc~ rides eni-~ t.].Pd its cor Ir ect, se o, uee~ t e rin.3 p~er tci be d et e Ir rmin ecl.. rl-le P 5 ''f'-~lU e oht~inec', w~s ~ in tl-l e fi IrS t c~se ~nd ;?0(~ in tt~e second. T,-,e bic)de.-!F~ .t/ility ~ ? tlle FiFCidU~:t W~3S veFy ~ood in e.~c,~ c~se ~ fter 28 clhys in the clo~.-.ec'~ ottle test)~
E ~mF~l e 7 /
5 " c~f rrl.-,ltose W~35 oxidised witl-l "yF,c,c"loFite by the rr,ethod deecribed in E}~.~rr,p:Le ~ n Two s~rr,F,les welre F~lrociuced~
one .O\f F,Fecipitation ~ t`Fom 5) and one by ev~.F,or-~tirin..
T,le PS W.-i5 ~20 f!~ the first s~rrlple ~nd 340 for- t,le second. T,~le pFociuct w~s Fe~dily hiode~r~d~ble in e~c,'~ c~se ~ % ~fteF 25 d~ys in t"e closed-~lottle test).
En~.rr~F 5 (Corr,F,~F~ti~e) Con,F.~.r~ti~e tests were c~.FFied L~Ut ~iy t,~,e o~ici~tion of 2~Y~i3 .;t.~r~ r~ -;r~liw~ qll dP~t~ y t,f~ rr,etl~ l de5~ d :in E~ r,~ Z arl d wi th ~5~ t-C~t il~ 0 f 5 nlo li?S O f ~ Li~r.i~ loLe i~ f l I L ~! C ~ i c~ l i. t. _ n fJ :i. tl-l rl-lf-~ u~ -- t d 1" i~ b o u t, ~ u ~ i d i ~- e li c t ~5.lcl-l w~
~ t ~ , e ~ d ,f~ c-~ lfiti~r:ir~l~ F~ C~ w e r , ~ ~ ~s~l!c~llt Z~J~i. -r ~l l?
prudllct was nL~i very biode~3l-aci.a~LL3 (~i~ dftelr Z~i d.5.ys in t h e ~ .l --hc! t t ] e tPSt)n In thl~ c~e uf cli ~tlri n wi th sep?l atiu71 c.~l-r ~ d uut :in the ~ a In e n ~ a 1 ~ n i? r, S' . ~ C1 1` 0 ~ :i cl :i 5 e d F:~ r o d u c t w ~ s F e r o v e r e d .e.r~
h ~d a s e quf~stLs t-i rl~3 puw 1.? r o f ~5. rl-, e p t- O d uc t ~I-u~w e d pu c~ r 1:! i. o cl ~? ~ lcl~5.~i :i :l ity (: ~: I X ;n .?~ f tf~ r c~ ~i cl .~ ~ ; :i rl t ~, e c ]. ci ~ d ---1 ! O t t l L
t e 5 t ! A
Tl-le st.:slrches used in tl-le pr'esent invellttion ~5~1~e prefet-abLy ~;tat-cl-lfn-~ ` ns~tur-c~l vel~et2ble C!rlyin r,~rr,pu5ed e~enti-llly of a~ylcise and 3rnyloFIectin~
rr~ r~ q }etelrl3Qnt COIllFlOsitiOns wet-e preFi~reci wi th the use of the proc1uct of E~anrlF,le 5 as o~tained hy direct eve.F,ir~ratiun without preciFIit~a~tion with ~lcu~lol.
The cleteryent curnpclsition w~s as follows:
Euilder- (E~n 5i100 part~ wt L~s (linear alF~yl SlllpihQnate.) Soap Non ioni c surfactant HT 1 'l 5 Tetraper borate (~leachin,~ a,3enti ~isilic~-5te Cat borlate 10 2 ~
Tlle c.lc~ e cc!rr,~ -.i.tion ~ tested :in ~-e-,pert r,f it, :ntl~-YIleFlo~iti.on -~.nd :~o~ rmr/.~l effel-.t ~.n,.l ~1ol~)eli 1 i ;a i.l ]. t; 5 .~ 1 1 t ~1 t. 1 1 0 i~ f ~ P r) t. ~ t .~ c. T I t. i i n 1 1. 1.1 li i. n ~-1 t, ~ ~ . n~ o -1' f` e .: t :i .. ~ e ~-, In o l.l n t o f t l-l c~ 0 ~J l_ .:,G I-le l t ~ d i. n ~ r:~ l Fl~ t ~ ~, n,-l ~ y l i r r i. cl .' m.~ :L e i ~ 5 t 1-1 e c- -f -f` e; t, :i ~f' ~e h l.l i 1 cl e lr ~
'' ''
Claims (11)
1. A mixture including oxidised glucosidic oligomers, comprising at least 60% by weight of glucosidic oligomers with degrees of polymerisation of from 2 to 10 obtainable by the hydrolytic demolition of starches and/or dextrin with endoenzymes and the oxidation of the enzymatic hydrolytic demolition product with an oxidising agent selected from hypochlorite and periodate in association with chlorite.
2. A mixture according to claim 1, comprising at least 75% of glucosidic oligomers with degrees of polymerisation of from 2 to 10, preferably from 2 to 8.
3. A mixture according to claim 2, obtainable by the oxidation of the hydrolytic demolition product with hypochlorite with a ratio of from 3-6 moles of hypochlorite/mole of glucoside units.
4. The use of mixtures including oxidised glucosidic oligomers according to claim 1 as builders for detergents.
5. The use of oxidised glucosidic oligomers with degrees of polymerisation of from 2 to 10, preferably from 2 to 8, and mixtures thereof as builders for detergents.
6. Use according to claim 5 in which the oligomers are selected from the group consisting of maltose and dimers, trimers and tetramers of maltose, oxidised with oxidising agents selected from hypochlorite and periodate.
7. A method of preparing a mixture of oxidised glucosidic oligomers useful as builders for detergents, comprising the hydrolytic demolition of starches and/or dextrin by endoenzymes to produce a mixture containing at least 60% by weight of oligomers having degrees of polymerisation of from 2 to 10 and the oxidation of the hydrolytic demolition product with hypochlorite or periodate in association with chlorite.
8. A method according to claim 7, in which the hydrolytic demolition product contains at least 755 by weight of oligomers with degrees of polymerisation of from 2 to 8.
9. A method according to claim 8, in which the oxidation is effected by sodium hypochlorite with a pH of from 8 to
10 and at a temperature of from 0 to 20°C.
10. A detergent composition comprising oxidised glucosidic oligomers with degree of polymerisation of from 2 to 10, preferably from 2 to 8 or mixtures thereof as the effective builder.
10. A detergent composition comprising oxidised glucosidic oligomers with degree of polymerisation of from 2 to 10, preferably from 2 to 8 or mixtures thereof as the effective builder.
11. A detergent composition comprising a mixture of oxidised glucosidic oligomers according to claim 1 as the effective builder.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT06763690A IT1249883B (en) | 1990-08-13 | 1990-08-13 | CALCIUM SEQUESTRING AGENTS BASED ON OXIDIZED CARBOHYDRATES AND THEIR USE AS BUILDER FOR DETERGENTS |
| IT67636-A/90 | 1990-08-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2048064A1 true CA2048064A1 (en) | 1992-02-14 |
Family
ID=11304100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002048064A Abandoned CA2048064A1 (en) | 1990-08-13 | 1991-07-29 | Calcium-sequestering agents based on oxidised carbohydrates and their use as builders for detergents |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0472042A1 (en) |
| JP (1) | JPH04233901A (en) |
| AU (1) | AU639193B2 (en) |
| CA (1) | CA2048064A1 (en) |
| IT (1) | IT1249883B (en) |
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|---|---|---|---|---|
| US7320887B2 (en) | 2001-10-31 | 2008-01-22 | Henkel Kommanditgesellschaft Auf Aktien | Alkaline protease variants |
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| US11155771B2 (en) | 2018-11-09 | 2021-10-26 | Henkel Ag & Co. Kgaa | Method for preparing a liquid washing or cleaning agent using a preservative-free dye solution |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE755050A (en) * | 1969-08-20 | 1971-02-19 | Unilever Nv | DETERGENT COMPOSITIONS |
| US3665000A (en) * | 1969-12-23 | 1972-05-23 | Fmc Corp | Tricarboxystarch derivatives |
| US4029590A (en) * | 1973-08-22 | 1977-06-14 | Fmc Corporation | Dextrin carboxylates and their use as detergent builders |
| US4113509A (en) * | 1975-05-14 | 1978-09-12 | Cpc International Inc. | Enzymatically produced maltose-maltotriose starch hydrolysate |
| US4113504A (en) * | 1977-10-03 | 1978-09-12 | Stauffer Chemical Company | Disposal of heavy metal containing sludge wastes |
-
1990
- 1990-08-13 IT IT06763690A patent/IT1249883B/en active IP Right Grant
-
1991
- 1991-07-26 AU AU81360/91A patent/AU639193B2/en not_active Expired - Fee Related
- 1991-07-29 CA CA002048064A patent/CA2048064A1/en not_active Abandoned
- 1991-08-05 EP EP91113154A patent/EP0472042A1/en not_active Withdrawn
- 1991-08-07 JP JP3197712A patent/JPH04233901A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7320887B2 (en) | 2001-10-31 | 2008-01-22 | Henkel Kommanditgesellschaft Auf Aktien | Alkaline protease variants |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1249883B (en) | 1995-03-30 |
| JPH04233901A (en) | 1992-08-21 |
| AU8136091A (en) | 1992-02-20 |
| AU639193B2 (en) | 1993-07-15 |
| EP0472042A1 (en) | 1992-02-26 |
| IT9067636A0 (en) | 1990-08-13 |
| IT9067636A1 (en) | 1992-02-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |